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Title: Ir 6In 32S 21, a polar, metal-rich semiconducting subchalcogenide

Abstract

Subchalcogenides are uncommon, and their chemical bonding results from an interplay between metal–metal and metal–chalcogenide interactions. Herein, we present Ir 6In 32S 21, a novel semiconducting subchalcogenide compound that crystallizes in a new structure type in the polar P31m space group, with unit cell parameters a = 13.9378(12) Å, c = 8.2316(8) Å, α = β = 90°, γ = 120°. The compound has a large band gap of 1.48(2) eV, and photoemission and Kelvin probe measurements corroborate this semiconducting behavior with a valence band maximum (VBM) of –4.95(5) eV, conduction band minimum of –3.47(5) eV, and a photoresponse shift of the Fermi level by ~0.2 eV in the presence of white light. X-ray absorption spectroscopy shows absorption edges for In and Ir do not indicate clear oxidation states, suggesting that the numerous coordination environments of Ir 6In 32S 21 make such assignments ambiguous. Electronic structure calculations confirm the semiconducting character with a nearly direct band gap, and electron localization function (ELF) analysis suggests that the origin of the gap is the result of electron transfer from the In atoms to the S 3p and Ir 5d orbitals. DFT calculations indicate that the average hole effective masses near the VBMmore » (1.19m e) are substantially smaller than the average electron masses near the CBM (2.51m e), an unusual feature for most semiconductors. The crystal and electronic structure of Ir 6In 32S 21, along with spectroscopic data, suggest that it is neither a true intermetallic nor a classical semiconductor, but somewhere in between those two extremes.« less

Authors:
ORCiD logo [1];  [1];  [1]; ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [4]; ORCiD logo [4];  [1]; ORCiD logo [1]
  1. Northwestern Univ., Evanston, IL (United States)
  2. Argonne National Lab. (ANL), Argonne, IL (United States)
  3. Univ. of Crete, Heraklion (Greece)
  4. Pennsylvania State Univ., University Park, PA (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
Air Force Research Laboratory (AFRL), Air Force Office of Scientific Research (AFOSR); National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Scientific User Facilities Division
OSTI Identifier:
1597262
Grant/Contract Number:  
AC02-06CH11357; DMR-1708254; N00014-18-1-2102; NSF NNCI-1542205; FA9550-19-1-0243; AC02-05CH11231; DMR-1807768; DMR-1420620
Resource Type:
Accepted Manuscript
Journal Name:
Chemical Science
Additional Journal Information:
Journal Volume: 11; Journal Issue: 3; Journal ID: ISSN 2041-6520
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Khoury, Jason F., He, Jiangang, Pfluger, Jonathan E., Hadar, Ido, Balasubramanian, Mahalingam, Stoumpos, Constantinos C., Zu, Rui, Gopalan, Venkatraman, Wolverton, Chris, and Kanatzidis, Mercouri G. Ir6In32S21, a polar, metal-rich semiconducting subchalcogenide. United States: N. p., 2019. Web. doi:10.1039/c9sc05609b.
Khoury, Jason F., He, Jiangang, Pfluger, Jonathan E., Hadar, Ido, Balasubramanian, Mahalingam, Stoumpos, Constantinos C., Zu, Rui, Gopalan, Venkatraman, Wolverton, Chris, & Kanatzidis, Mercouri G. Ir6In32S21, a polar, metal-rich semiconducting subchalcogenide. United States. doi:10.1039/c9sc05609b.
Khoury, Jason F., He, Jiangang, Pfluger, Jonathan E., Hadar, Ido, Balasubramanian, Mahalingam, Stoumpos, Constantinos C., Zu, Rui, Gopalan, Venkatraman, Wolverton, Chris, and Kanatzidis, Mercouri G. Tue . "Ir6In32S21, a polar, metal-rich semiconducting subchalcogenide". United States. doi:10.1039/c9sc05609b. https://www.osti.gov/servlets/purl/1597262.
@article{osti_1597262,
title = {Ir6In32S21, a polar, metal-rich semiconducting subchalcogenide},
author = {Khoury, Jason F. and He, Jiangang and Pfluger, Jonathan E. and Hadar, Ido and Balasubramanian, Mahalingam and Stoumpos, Constantinos C. and Zu, Rui and Gopalan, Venkatraman and Wolverton, Chris and Kanatzidis, Mercouri G.},
abstractNote = {Subchalcogenides are uncommon, and their chemical bonding results from an interplay between metal–metal and metal–chalcogenide interactions. Herein, we present Ir6In32S21, a novel semiconducting subchalcogenide compound that crystallizes in a new structure type in the polar P31m space group, with unit cell parameters a = 13.9378(12) Å, c = 8.2316(8) Å, α = β = 90°, γ = 120°. The compound has a large band gap of 1.48(2) eV, and photoemission and Kelvin probe measurements corroborate this semiconducting behavior with a valence band maximum (VBM) of –4.95(5) eV, conduction band minimum of –3.47(5) eV, and a photoresponse shift of the Fermi level by ~0.2 eV in the presence of white light. X-ray absorption spectroscopy shows absorption edges for In and Ir do not indicate clear oxidation states, suggesting that the numerous coordination environments of Ir6In32S21 make such assignments ambiguous. Electronic structure calculations confirm the semiconducting character with a nearly direct band gap, and electron localization function (ELF) analysis suggests that the origin of the gap is the result of electron transfer from the In atoms to the S 3p and Ir 5d orbitals. DFT calculations indicate that the average hole effective masses near the VBM (1.19me) are substantially smaller than the average electron masses near the CBM (2.51me), an unusual feature for most semiconductors. The crystal and electronic structure of Ir6In32S21, along with spectroscopic data, suggest that it is neither a true intermetallic nor a classical semiconductor, but somewhere in between those two extremes.},
doi = {10.1039/c9sc05609b},
journal = {Chemical Science},
number = 3,
volume = 11,
place = {United States},
year = {2019},
month = {12}
}

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